Photosensitive resinous compositions and photographic elements



United States Pate t This invention relates to photography and, more particularly, to novel compositions comprised of photosensitive material and certain synthetic resinous copolymers of certain vinylidene compounds with copolymerizable dicarboxy compounds, which copolymers have both carboxylic ester and carboxylic acid groups. The compositions of this invention are particularly useful for coating a surface intended to receive a photographic reproduction of a latent or visual image. The invention includes photographic elements which are represented by a surface having a coating of one or more layers of a novel composition of this invention. The invention also embraces printing, developing, and fixing the images which are reproduced, using the novel compositions of this invention.

The term photosensitive material, as used herein in the specification and claims, defines single chemical compounds or mixtures of chemical compounds which are chemically affected by the action of a part or all of the radiant energy in that portion of the electromagnetic spectrum between and including infrared and X-rays. Accordingly, the term photographic is used herein to define the reproduction of images by the action of such radiant energy upon photosensitive material.

In that portion of the graphic arts industry as represented by photography, photoengraving, photolithography, collotypy, etc., gelatin, albumin, polyvinyl alcohol, cellulose nitrate, and certain other natural and synthetic polymeric materials have been used, either alone or in some combination, as the carrier for photosensitive materials in the preparation of a photosensitive layer of a photographic element. Because of the peculiar requirements of photographic reproduction processes, gelatin or albumin have remained as the principal carriers or binding agents for photosensitive materials in the photosensitive layers. Any undeveloped photosensitive coatings which contain these natural materials as the principal carriers, must be protected from moisture during use and are unstable at high or low temperatures, which limit their use in certain climates and require that costly packaging methods be used. Furthermore, developed and fixed photosensitive coatings in which these natural materials are the principal binding agents or carriers, have relatively poor abrasion-resistance and are susceptible to attack by biological organisms such as fungi. In addition, many of the coating solutions, whether the carrier or binding agent be gelatin, albumin, polyvinyl acetate, or polyvinyl alcohol, contain relatively large quantities of water, necessitating a lengthy drying step to remove this water as a part of the procedure for forming a photosensitive layer on a base material.

An object of this invention is to provide new and useful photosensitive compositions which are stable, of little or no water content, and can be used to provide smooth, tough, abrasion-resistant, and tightly adherent photosensitive coatings on surfaces of glass, metal, films of synthetic resin, wood, paper, and the like. A further object is to provide photosensitive compositions which are easily applied to such surfaces, fast drying, not softened by water or attacked by acid, and have good adherence to Water-resistant and hard-to-coat surfaces. A further object is to provide photographic elements with water-insoluble photosensitive layers which are fast printing and different methods.

ICC

can be processed rapidly in alkaline developing mediums" to yield reproductions of high contrast, resolving power, and definition.

The above objects are attained by the preparation and use of the novel compositions of this invention, which.

are comprised of a photosensitive material and a resinous copolymer of certain vinylidene compounds with afi-elllylenically unsaturated dicarboxy compounds, which copolymer has both carboxylic acid and certain carboxylic,

ester groups.

The novel photosensitive compositions of this inven tion lend themselves to simple and reproducible application procedures to surfaces of glass, metal, films of synthetic resins and other commonly used film supports. After exposure, coatings of the photosensitive compositions of this inventioncan be swollen to allow penetration of processing solutions without permanent impairment of the strength, toughness, or permanence of the coating. Coatings of these compositions show minimum distortion during processing and use. A particular feature of the novel compositions of this invention is that the photographic elements prepared therefrom can be prepared to respond to photochemical and photomechanical development processes.

In the practice of this invention, resinous copolymers can be used where the vinylidene compounds are vinyl esters such as vinyl acetate, vinyl propionate, vinyl bu-.

tyrate, vinyl stearate, vinyl benzoate, etc.; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl n-octyl ether, etc.; vinylidene halides such as vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, trifluoroethylene, tetrafluoroethylene, etc.; vinylidene cyanides such as acrylonitrile, methacrylonitrile, ethacrylonitrile, etc.

. In the preparation of the resinous copolymers, the vinylidene compound is polymerized with an alpha-, betaethylenically unsaturated dicarboxy compound, such as maleic anhydride, maleic acid, fumaric acid, citraconic acid, itaconic acid, and half-esters (i.e., acid esters) of these acids and mixtures thereof.

7 It is required that the resinous copolymers to be used in the practice of our invention contain both carboxylic acid and certain carboxylic esters groups, with the further requirement that 590% of the total of these carboxy groups be particular carboxylic ester groups. Prefer! ably, from about 10% 'to about 60% of the total of these carboxy groups are carboxylic ester groups. The preparation of these resinous copolymers having both carboxylic acid and carboxylic ester groups in the re quired proportion, can be accomplished by a number of- For example, the vinylidene compound can becopolymerized with maleic anhydride and the resulting copolymer subjected to controlled partial esterification to yield a resinous copolymer having both carboxylic acid and carboxylic ester groups in the desired proportion. While this controlled partial esterification canbe accomplished after the copolymer of the vi nylidene compound and maleic anhydride has been completelyprepared, there are techniques known to the art whereby the controlled partial esterification is carried out simultaneously with the step for the copolymeriz'atio'n of vinylidene compound and maleic anhydride. An alternative method is to polymerize the vinylidene compound with a dicarboxy compound in which one of the carboxy groups is a carboxylic ester group, such as half-ester of maleic or fumaric acids. When this method-is followed, it will be understood that, in the resulting resinous copolymer, half of the carboxy groups will be carboxylic acid groups and the other half of the carboxy groups will be carboxylic ester groups. Another alternative method is to copolymerizethe vinylidene compound with an alpha-, beta-unsaturated dicarboxy compound in which Patented June 27, 1961 bdtlibf theca'rboxy groups are carboxylic ester groups,

to 'produce a resinous copolymer in which substantially allof the carboxy groups present are carboxylic ester groups, and thereafter subjecting this esterified copolynier'to controlled partial hydrolysis so as to-hydrolyze" only a-portion of the ester groups to yield a'copolymer containing both carboxylic acid and carboxylic ester groups in the desired proportion. The final resinous cop'olymer containing both the carboxylic acid and the carboxylic ester groups in the desired proportion, canc'ontaina small proportion of polymer units in which the carboxy'groups have notbeen'esterified. For example,

when maleic anhydride is used as a copolymerizingmono mer, theresulting resinous copolymer can contain copoly mer units in which the maleic anhydride heterocycle'is notbrokenor in which both of the carboxy groups are carboxylic acid groups even after the resinous copolymer, as a mass, has been subjected to controlled partial oi o" alcohols generally containing 7 to 17 carbon atoms;

othersuitable aliphatic ester groups are alkoxy alkyl ester groups, such as methoxyethyl, 2-ethoxyethyl, and 2-butoxyethyl groups; unsaturated aliphatic ester groups afr'e also suitable, such as allyl, methallyl, and propargyl ester groups; aromatic ca'rboxylic ester groups are also suitable, such as the'phenyl, phenylethyl, phenylpropyl, and benzyl ester groups; cycloaliphatic carboxylic ester groups are also -suitable,such as the cyclopentyl and'cyclo heirylester groups. I

'It will be clear from the foregoing and the numerous examples cited hereinafter that the term carboXylic ester group means the ester group formed by the esterification of the carboxyl group of the m,{3-ethylenically unsaturated dicarboxylic acidywith a monohydroxy compound of the above-listed illustrative-'materials, i.e. aliphatic alcohols, alkoxy alkanols, aromatic alcohols, and cycloaliphatic alcohols.

.The resinous copolymers to be used in the practice of our invention should have a molecular weight of from about 1,000 to about 600,000. The preferred resinous copolymers are those having molecular weights within the rangeof from about 20,000 to about 300,000. As used herein, the molecular weight of a resinous copolymeris'to be understood to mean the Weight average-molecular weight as determined by the Staudinger method. In generaL- suitable resinous copolymers are prepared by copolymerizi'ng one mol proportion of the vinylidene compound with one'mol proportion of the alpha-, betaethylenically unsaturated dicarboxy compound. We find that maleic anhydride and the half-esters of maleic acid are preferred dicarboxy monomers for the preparation of the resinous copolymers to be used in the practice of our invention. 7 H

Specific examplesof resinous copolymers which are representative of those suitable for use in the practice of our invention will be described briefly, however the invention is notlimited to the use of these specific resinous copolymers:

(1) Resinous copolymer having a molecular weight of about 100,000, prepared by the copolymerization of equal mol proportions of vinyl acetate and maleic anhydride, which copolymer has been partially esterified so that approximately 70% of the carboxy groups are carbonylic acid groups and 30% of the carboxy groups, are benzyl 'carboxylic ester groups. p Y '(2 )f R"esirious copolymer having a'molecular weight of 2:50;000,fpr'epared byth e copolymerizationof one mol of vinyl acetate with 0.5 mol of maleic anhydride and 0.5 mol of thebutyl half-ester of maleic acid.

(3) Resinous copolymer having a molecular weight of about 25,000, prepared by the copolymerization of equal mol proportions of vinyl acetate and maleic anhydride, which copolymer hasbeen partially esterified so that about 70% of the carboxy' groups. are carboxylic" acid groups and 30% of the carboxy group's 'are'icarboxylicr Y ester groups derived from a 50/50 mixture of allyl a1:

cohol and ethyl alcohol.

(4) Resinous copolymer having a molecularweight'pf about 20,000, prepared by the copolymerization of equal mol proportions of vinyl acetate and the Z-ethylhexyl half-ester of maleic acid.

(5) Resinous copolymer having a molecular weight of about 45 ,000,- prepared by the copolymerization of equal mol proportions of vinyl acetate and maleic anhydride,

which copolymer has been-esterified with about 1.6 mol proportion of cyclohexanol so that about 20% of the car-- boxy groups are carboxylic acid groups and 80% of the; carboxy groups are cyclohexyl carboxylic ester groups...

(6) Resinous copolymer having a molecular weight ofabout 60,000, prepared by the copolymerization of 0.5 mol proportion of vinyl'methyl ether, 0.2 mol proportion:

of maleic anhydride, and 0.3 mol proportion of the tetradecyl half-ester of maleic acid.

(7 Resinous copolymer having amolecular weight 0 I about 20,000, prepared by copolymerizing about 0.8 mol proportion of vinyl ethyl ether with about one mol proportion of maleic'anhydride, and subsequent partial esterification with about 0.4 mol proportion of cyclohexanol.

(8) Resinous copolymer having a molecular weight of:

about 30,-00.0, prepared bycopolymerizing equal mol pro portions of vinyl methyl ether and maleic anhydride, which copolymer has been partially esterified wlthabout one mol proportion of 0x0 alcohol having 10 carbon.

atoms.

(9) Resinous copolymer having a molecular weight of about 30,000, prepared by the copolymerization'of equal:

mol proportions of vinyl acetate and a half-ester of maleic acid, in which the ester groups are derived from 0x0 alcohols having '8 carbon atoms.

' (l0) Resinous copolymer having a molecular weight of about. 150,000, prepared by the copolymerization of groupstocarboxylic acid groups.

('12) Resinous copolymer having a molecular weight of about 60,000, prepared by the copolymerization of 0.5 mol proportion of vinylidene chloride, 0.25 mol proportion of maleic anhydride, and 0.25 mol proportion of the benzyl half-ester of-maleic acid.

(13) Resinous copolymer having a molecular weight of about 50,000, prepared by the copolymerization of mol proportion of vinyl chloride and one molpro'po'rtion of maleic anhydr'ide, whichcopolymer has been partially esterified with butanol, whereby'30% of the total of the carboxy groups are converted to butyl carboxylic ester groups and the remaining 70% of the carboxy groups are carboxylic acid groups.

(14) Rcsinouscopolymer having a molecular weight of about 30,000, prepared by the copolymerization of about one molproportionof acrylonitrile with about onemol proportion of the cycloheXylhalf-ester of maleic acid.

(15) 'Resinous copolymer having a molecular weight at about 80,000, prepared by the copolymerization of equal rnol proportions of methacrylonitrile' and the neoctyl half-jesterjotmaleic acid.

' (16) Resinous copolymer having a molecular weight or about 120,000, prepared by the copolymerization of equal mol proportions of vinyl ethyl ether and the ben zyl half-ester of maleic acid.

(17) Resinous copolymer having a molecular weight of about 15,000, prepared by the copolymerization of equal mol proportions of acrylonitrile and the beuzyl half-ester of maleic acid.

(18) Resinous copolymer having a molecularweight of about 40,000, prepared by the copolymerization of equal mol proportions of acrylonitrile and the x0 halfester of maleic acid, which half-ester is prepared by the reaction of a C oxo" alcohol with maleic anhydride. (19)" Resinous copolymer having a molecular weight of about 30,000, prepared by the copolymerization of equal mol proportions of vinyl ethyl ether and 2-ethylhexyl half-ester of maleic acid.

(20) Resinous copolymer having a molecular weight of about 60,000, prepared by the copolymerizationof about one mol proportion of vinyl chloride with about one mol proportion of the n-octyl half-ester of maleic acid.

.The resinous copolymers used in this invention may be prepared by various methods known to those skilled in the art of preparing synthetic resins by the copolymerization of these monomers. The copolymers can be prepared by reacting and polymerizing the vinylidene compound with suitable alpha-, beta-ethylenically unsaturated dicarboxy compound by conventional polymerization methods, as, for example, by heating, exposing to actinic light,

or by the use of polymerization catalysts or any combination of these polymerization accelerators, in mass, in solution, or in suspension or in emulsion in water or a nonsolvent. The copolymers so formed are then generally reacted with the selected alcohol or mixture of alcohols to partially esterify the available carboxy groups.

Photosensitive material useful in the novel composition of this invention, broadly speaking, include the lightsensitive diazo compounds such as those obtained by diazotization of asymmetric n-alkyl or aryl p-phenylene diamines, the anilides of dialkoxy phenylene diamines, the diazo-oxides and imides of such compounds, and others which are hereinafter described in greater detail; dichromates such as ammonium dichromate, potassium dichromate, etc.; iron systems such as mixtures of ferric ampler is present in the developing bath, or of the two-component type, wherein both diazo and coupler are present in the light-sensitive composition.

The light-sensitive diazo compounds most commonly used include those prepared from the following amines:

R; Y Y

R; Z X Z X Y R10 0 NEG-NH:

wherein R and R are organic radicals, e.g., aliphatic ihydrocarbon, aromatic hydrocarbon, heterocyclic, etc.;

also, R and R together may form a saturated, unsaturated, or heterocyclic ring. R may be the same as R or maybe 4R1, OR1, OI X and Y,may be H, Cl, Br, alkyl, aryl, alkoxy, arloxy, haloalkyl, etc. Z is a hydrogen, or together with X, may forma heterocyclic or aromatic ring. Specific compounds of this type include p-aminoacetanilide, p-aminobenzani- Diand trihydric phenols, e.g., resorcinol, phlorglucinol Alphaand beta-naphthol 1-naphthol-3,8-disulfonic acid 1,8-dihydroxynaphthalene-3,6-disulfonic acid 2-naphthol-6,8-disulfonic acid 2'-naphthol-3,6-disulfonic acid 2,3-dihydroxynaphthalene 2,3-dihydroxynaphthalene-6-sulfonic acid Acetoacetanilide and its substitution products Phenylmethylpyrazolone and its substitution products Amides of 2-hydroxy-3-naphthoic acid, e.g., the anilide,

S-methanilide, alpha-naphthylamide, beta-naphthylamide, and 4-phenylanilide.

Although aromatic amino coupling components cannot be added to the light-sensitive solutions since they react to form dyes even in acidic solution, they may be employed in the developer solution. Such compounds are aniline, naphthylamines, aminophenols, and aminonaph- .thols, unsubstituted or having substituents in the ring or in the amino groups, e.g., o-toluene n-aminophenol, 1-amino-8-naphthol-3,6-disulfonic acid, etc.

There can be added to the compositions containing diazo compounds, various stabilizers such as urea, thiourea, allyl thiourea; inorganic acids such as boric, fluoboric; inorganic salt such as zinc chloride; and salts of organic acids such as tin, zinc, or cadmium salts of weak organic acids as tartaric, citric, succinic, etc. Pigments, opacifiers, and flatteners, such as titanium dioxide, alumina, silica, etc., can be employed in the compositions to improve contrast or to change texture.

Compounds which prevent decomposition of the lightsensitive diazonium compounds when coated on metal plates are, for example, corrosion inhibitors and metal deactivators, such as tricresyl phosphate, didodecyl phosphate, sodium nitrate, and amyl nitrate, etc. These compounds can be added in small amounts, i.e., from about 0.01% to 0.2% by weight of the resin used.

When systems other than those employing diazo compounds, such as those involving silver halides, are used, 'modifying adjuvants such as dyes which modify the Optical sensitivity of silver halide, e.g., the cyanine'dyes, including carbocyanine, merocyanine, neocyanine, etc., other dyes, antifogging agents, pigments, and the like, can be added. 7

If desired, plasticizers can be incorporated into the photosensitive compositions to increase the flexibility of the photosensitive compositions when used as a film applied to a supporting surface. The incorporation of'a plasticizer is particularly important when it is desired to make the photosensitive composition into the form of a free film. Flexible or pliable free films of the photosensitive compositions of this invention are particularly useful in cartographic work where it is frequently necessary to stretch or otherwise distort the film (as after a visible image has been developed) to bring the image into register with the master chart. Also, where plates having relief images are being prepared for multicolor printing, stretchability of the supporting base and the relief image is desirable to bring the plates into register for the successive printing of the different colors. Suitable plasticizers include the phthalate esters, for example, di-Z-ethylhexyl phthalate, dimethyl phthalate, dimethyl- .Qellosolve pnthalate, as well as other plasticizing esters such as methyl phthalylethyl glycolate, dimethyl adiphate, .dibuityl sebacate, and also glycols and glyc l etherssuch ethylene glycol, hexamethylene glycol, polyethylene glycols, etc. In general, amounts of plasticizer up to about 50% by weight based on the total content of the composition can be used. 7

Other resins (natural or synthetic) can be incorporated into the photosensitive compositions to increase the waterinsolubility of the compositions. These resins most desirably are-hydrophobic in character and compatible with the particular copolyirier selected from those herein described. Such additional resins are, for example, nitrocellulose, cellulose acetate, polyvinyl acetate, methylcellulose, etc. These resins can be used in amounts upto one part of the compatible resin per one part of a desired resinous copolymer.

Cross-linking agents can also be added to the photosensitive composition or to the developing solution, in which case the desired degree of insolubilization is generally obtained by subjecting the photographic element to radiant heat. Cross-linking agents which react with the carboxyl groups of the resinous oopolymers to produce insoluble clear are, for example, formaldehyde polyfunctional hydroxy or amino compounds, such as ethylene diamine, ethanolamine, polyglycols, polyvinyl alcohol, etc.

The photosensitive compositions of this invention are particularly useful for coating a surface intended to receive a photographic reproduction of a latent or visual image. These photosensitive compositions are most conveniently applied to such surfaces as solutions of the photosensitive composition in a mutual solvent. The term mutual solvent, as used herein, means a solvent or solvent rm'xture which will dissolve the other components of the photosensitive composition. The novel photosensitive layers or photographic elements produced therefrom by the complete or substantial removal of the mutual solvent during the coating operation, comprise a stratum which is composed essentially of the herein-described partially esterified resinous copolymer and photosensitive material. Since organic solvents may be used, the drying time normally necessary with photosensitive coatings ,canbegreatly reduced. However, a small amount of water may be present in the solvent mixture to aid in dissolving certain of the photosensitive material used. The coating solutions can be prepared by dissolving the resinous copolymer and photosensitive material in the mutual solvent. As exemplary of mutual solvents which may be used in one or more of the combinations of this invention are: Esters such as methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, ethyl glycolate, etc.; alcohols such as ethanol, iso-propanol, n-butanol, sec.- butanol, etc; ketones such as acetone, methylethyl ketone, cyclohexanone, etc. 7 p

Where water is required to dissolve the photosensitive component, solvents or solvent solutions which are water- ,miscible to the extent of 10% or more of water, are

preferred. Further, it is usually desirable to use organic solvents which have anappreciable vapor pressure at normal temperatures, so that drying times will be as short as possible.

The resinousester and the photosensitive material can be dissolved; separately in the same solution, or dissolved in different portionsof the same solvent, or in separate miscible solvents, as, for example, dissolving the photosensitive material in water and the resinous ester in acetone and mixing the two solutions. Other constituents commonly employed with certain photosensitive materials can be addedin like manner. The resultingsolutions may then be applied to a support and theresulting layers dried. It should be noted that, in

the preparation of the solutions and the coating operations radiations which. affect the photosensitive r 1$l e fiwi Coating compositions which are comprised of'photosensitive material, the described resinouscopolymcr, and amutual solvent, for ease of application, should be prepared so as to have a solids content ie; photosensitive material'plus the'resinous copolymeryof between 1% and 20%. However, we have found that the more suitable coatings for those solutions having such a solids content within the range of 710%, depend uponthe particular resin employed and the method of application. Any of the conventional methods of coating or application may be used to apply coatings of the photosensitive composition, such as brushing, dipping, roller coating, or spraying. For spraying, it is usually desirable to use a dilute solution containing a high percentage of a volatile solvent, while for dipping and brushing, higher solids content may be employed. Furthermore, for roller coating or doctor-knife coating, still higher solids content compositions may be employed. The advantageous properties of the photosensitive compositions of this invention are generally realized when the ratio of photosensitive material to resin is in the range of 1:2 to 1:40 parts by weight.

The photosensitive coating compositions of this invention have the advantages that they are easily prepared and can be applied by any of these conventional application procedures to any water-resistant surface, such as polyester glass cloth (a glass fiber polyester laminate having a thickness of about 5 mils, generally made by impregnating a single or multiple ply web of woven or .nor'nwoven glass fiber with a thermosetting polyester resin, such as polymerized styrenated diethylene glycol maleate), glass, metals such as aluminum, zinc, copper, carbon steel, stainless steel, iron, magnesium, or plastic films such as cellulose acetate, cellulose propionate, cellulose nitrate, cellulose acetate-butyrate, polyethylene terephthalate (sold under the trademark Mylar by du Pont de Nemours), as well as to other conventional surfaces, such as paper, wood, composition board, etc. The coatings of these photosensitive compositions are smooth, tough, and waterand acid-resistant. Accordingly, the careful handling procedures which the graphic arts industry has been forced to follow in the past, can now be virtually eliminated by the use of the photosensitive coatings of this invention.

The speed at which the coating dries is naturally dependent on the solvent used, the concentration of the solution, and the application method. When the spray method is used, the coating dries almost instantaneously; when other methods are used, drying may be facilitated by passing a current of hot air over the surface.

The compositions of this invention have a wide utility and are generally useful in the graphic arts, wherein a reproduction of a drawing, design, plan, etc., is desired. Thus, in the manufacture of templates for use in preparing parts of airplanes, automobiles, boats, radio and electrical equipment, etc., the materials to be used, such as steel, aluminum, etc., are coated with the light-sensitive compositions of this invention, dried, exposed through the master drawing, and developed. The finished print is an exact reproduction of the original and adheres firmly to the metal or other material. Stencils or lettered transparencies may also be used to reproduce directions, identification numbers, etc., on parts or finished articles of manufacture. The photosensitive film elements of the present invention may also be used as print stock in the production of black and white prints.

A particular feature of some of the novel compositions -of-this invention is that the photographic elements prepared therefrom can be used for both photochemical and Thus, not only those compositions containing ammonium or alkali metal bichromates as the light-sensitive material, but also those containing diazo compounds, can be used t o obtain mechanical images, by rendering the composition insoluble or altering its surface in proportion to the'eiof the image and non-image areas. Alternatively, devel-' opment may be accomplished by treatment with a solution containing a solvent for the unchanged resin, producing differential swelling or solution as above. These compositions, which are susceptible to photomechanical reproduction, are useful as the photosensitive coating in preparing resist images on printing supports, such as aluminum, zinc, copper, and magnesium, various alloys thereof, and non-metallic supports such as paper, cloth, or plastics. When these coatings on such supports are exposed to the actinic radiations to which the particular coating is responsive, the coating is rendered insoluble in proportion to the action of light thereon, and an image is developable therein. In general, the areas receiving the most actinic radiation are insolubilized relative to those receiving less exposure, and remain on the support when the coating is treated with solvents for the lesser exposed portions of the coating, leaving uncoated areas permitting subsequent etching, dyeing, or other treatment of the exposed substrate. The resulting plates can be used in the appropriate intaglio, planographic, or relief printing processes.

Further details of the practice of this invention are set forth with respect to the following specific examples, in which all parts are by weight unless specified other wise: I

Example 1 Two solutions are prepared as follows:

. Parts Methylethyl ketone 450 Resinous copolymer having a molecular weight of about 50,000, prepared by the polymerization of equal mol proportions of vinyl acetate and maleic anhydride and esterifying 20% of the available carboxy groups with methyl alcohol 50 Di-Z-ethylhexyl phthalate 6 Methylethyl ketone 225 p-Diethylaminobenzene diazonium fluoborate 8 acetate positive test sheet containing lines, numerals, and

Ben Day in five difierent reductions, is placed in contact with the photosensitive coating and placed thirty inches from an uncoated carbon arc lamp, and then exposed for one minute. A developing solution is prepared from one part of resorcinol, parts of sodium carbonate, and 200 parts of water, and the exposed coated glass cloth is immersed in this developing solution for a period of one minute, followed by a water wash and immersion in a 5% acetic acid solution. A sharp, black image is thereby produced upon the coated surface of the polyester glass cloth, which is a positive reproduction of the lines, numerals, and Ben Day of the test sheet. The surface bearing the image is smooth, hard, and mar resistant.

h 10 Example 2 Two solutions are prepared as follows:

Methylethyl keton Resinous copolymer prepared by'the copolymerization of equal mol proportions of vinyl acetate and half-ester of 'maleic acid, which copolymer has a molecular weight ofabout 100,000, and wherein of the ester groups are derived from butanol and the other A from methanol 55 Di-2-ethylhexyl phthalate Zinc chloride double salt of 3-chloro-4-diethylaminobenzene diazonium chloride 8 Water 30 30% phosphorous acid (sp. gr. 1.12) 16 Aceton A 'sprayable solution is obtained by mixing 5 volumes of solution (C) -with.one volume of solution (D).

An 8" x 10" polyester glass cloth is spray coated with the above photosensitive composition, exposed, developed, and fixed as in Example 1. The reproduction so obtained One volume of solution (E) is mixed with 5 volumes of solution (C). The composition is then coated on an 8" x 10 polyester glass cloth sheet, dried and contact exposed with a test sheet in sunlight until visual bleaching occurs in the non-image areas' (30 seconds in strong sunlight). The filmis then immersed in a developing solution composed of onepart of phloroglucinol, 5 parts of sodium carbonate, 20 parts of acetone, and 250 parts of water, for a period of one minute. The film isthen dipped in a 5% acetic acid solution, washed thoroughly with water, and wiped dry. There is obtained a clear positive reproduction of the test sheet.

Example 4 i A solution is prepared as follows:

Parts 4-N-phenylaminobenzene diazonium fluoborate 8 Methylethyl ketone 225 Example 5 I The photosensitive composition of Example 1 is sprayed on a supporting surface of each of the following materials: Glass, aluminum, and Mylar polyethylene terephthalate. The photosensitive elements so prepared are then exposed,- developed, and fixed as in Example 1, yieldinga clear, sharp reproduction of the test sheet lines and numerals.

The coating is smooth and-uniform and exhibits good ad-' hesion, dry and wet.

mol proportions of vinyl acetate and the cycloheXyl halfester of maleic acid.

(3) Resinous copolymer; having a molecular weight of about 100,000, prepared ,bythecopolymerization of vinyl acetate audhmaleic .anhydride, which copolymer has been partially estcrified sogthat about 20% of the carboxyl groups are carboxylic acid groups and 80% of the carboxy groups are Z-ethylhexyl carboxylic ester groups.

(4) Resinous copolymer having a molecular weight of about,80,000, prepared by the 'copolymerization of equal mol proportions of vinyl acetate and the benzyl half-ester of maleicacid.

(5) Resinous copolymer having a molecular weight of about 200,000, prepared by the 'copolymerization of equal mol proportions of vinyl ethyl ether and the cyclohexyl half-ester of maleic acid.

(6) Resinous copolymer-having a molecular weight of about 60,000, prepared by the copolymerization of equal mol proportions of vinyl chloride and diethyl maleate, followed by hydrolysis of 30% of the ester groups, leaving 70% carboxylic ester groups in said copolymer.

. (7) Resinous copolymerhavingamolecular weight of about 70,000, prepared by thecopolytneriz'ation of equal mol proportions of vinyl methyl ether and the benzyl halfester of inaleic acid; j

, (8) Resinouscopolymer having a molecular weight of about"40,000, prepared by the copolymerization of equal mol'proportions of vinyl'chloride andthe benzyl halfester of maleic acid.

a (9) Resinous copolymer having a molecular weight of about 15,000, prepared by the copolymerization-of equal mol proportions of acrylonitrile and the benzyl half-ester of maleic acid.

(10) Resinous copolymer having amoleculai' weight of about 10,000, prepared by the 'copolymerization of equal. mol proportions of acrylonit'r'ile and the cyclohexyl half ester of maleic acid. 1

(11) Resinous copolymer having a molecular weight of about 40,000, prepared by the'copolymerization of equal mol proportions of methacrylonitrile and the C oxo half-mter of maleic acid.

('12) Resinous copolymer having-a molecular weight of-about 20,000, prepared by the copolymerization of equal mol proportions of vinyl chloride and maleic anhyd'ride, which-copolymer has been partially-esten'fied with 0.9 inol proportion of ethyl alcohol.

-(l3) Resinous copolymer-having a molecular weight of about 30,000, prepared by the 'copolymerization of equal molproportions of vinyl'chloride and the cyclohxyl half-ester of maleicacid.

f (14) Resinous-copolymer having a molecular weight of-"about 70,000, prepared by the copolymerization of equal mol proportions of vinyl acetate and the tetradecyl' half-ester of maleic acid.-

(l5) Resinous copolymer having a molecular weight of about 20,000, prepared by'the'copolymerizaition of 0.5 mol proportion of vinyl acetate, 0.25 mol proportion of maleic" anhydride, and 025 mol proportion of n-butyl half-ester of maleic acid. 7

. (IQ-Resinous copolymer'having a molecular weight o--'about40,000; prepared by'the copolymerizationof equal: mol proportions of vinyl acetate and maleic anhydride, which copolymer has;been pa'rtially. esterified with-a mixture of 0.30 mol of allyl alcohol and 0.50 mol;

of ethyl alcohol ,(17) Resiuouscopolymerthaving a molecular-weight of; about l50,000, prepared by the'co'polymerization of equal mol yproportionsof vinyl acetate and the iso-propyl half;

ester of maleic acid. e

. (18') Resinous copolymer having a molecular weight 6:

about 300,000, prepared by the copolymerization-of equal mol proportions of 2-ethoxyethyl vinyl ether and maleic. anhydride; which copolymerhas been partially esterified; with 0.7 mol of Z-ethylhexanol. v 1 1 r V I Example I A solution of the following composition is prepared:

- Pans Methylethyl ketone l Resinous" copolymer having a V olecular Weightot- "about 300,000, prepared by the copolymerization of equal mol proportions of vinyl acetate'an'd' -maleic anhydride in the presence of 0.36 mol methanol, so'tliat 18% of the total carboxy groups inthe polymer 'are present as carboxymethyl groups 20 p-Diethylaminob'enzfene diaz onium fluoborate 1 The solution is flow-coated. on polyester glass cloth sheet, hung in a vertical position to drainbriefly, and drying is assisted with .a blast of. air. -About 1.5 g per 80- sq. in; of dry coating is thus deposited. The. coated .filmisexposed. behind a cellulose acetate test positive bearing lines, numerals, solids, and benday in five different reductions, at a: distance of thirtyinches from a carbon arc lamp forone minute. The exposed film is immersed for one. minute in a developing solution composed of resorcinol, 1 part; methyl phloroglucinol, l part; sodium carbonate, 5 parts; water, 200 partsyand alcohol, 20 parts. The film is then immersed briefly in a 5% acetic acid solution, rinsed in water, and dried." A sharp, dark-brown image is thereby produced within the coating on the polyester glass cloth which is a positive reproduction of the images on'the test sheet. 1

Example 8 A solutionis prepared as follows:

Parts Methylethyl keton Resinous copolymer preparedby the copolymeriz'ation of equal mol proportions of vinyl acetate and a half-ester of maleic acid, which copolymer has a molecular Weight of about 60,000 and wherein p of-the ester'groups'are derived from butanol and the other A from methanol. 20 Zincchloride double salt of 3-chloro4-dimethylamino-benzene diazonium chloride 1 Water Y 5' The solution is coated on polyester glass cloth using a Boston-Bradley doctor blade at a setting of 0.009 inch. The film is allowed to dry in a horizontal position and is then exposed and developed as in Example 7. The reproduction so obtained has a deep orange image of good contrast.

Example 9 13 A polyester glass cloth sheet is coated, dried, exposed, and developed as in Example 7. A red-brown image is obtained. a Example 10 A solution was prepared as follows:

Parts Methylethyl ketone 1,80 The resinous copolymer of Example 8 20 p-Diethylaminobenzene diazonium fluoroborate i 1 Triaminotoluene trihydrochloride 0.5

The solution is coated on polyester glass cloth and allowed to dry, then exposed under a positive to sunlight for one minute. The film is exposed to moist ammonia vapor by holding it over a bottle of concentrated aqueous ammonia. A sharp, dark red-brown image appearsimmediately.

Twenty volumes of solution 1 are mixed with one volume of solution 2, and a sheet of polyester glass cloth is then coated with the mixture and dried. The film is exposed under a positive to sunlight for two minutes, then developed in a 10% solution of potassium ferricyanide in water. A white image on a deep blue background is produced.

Example 12 The procedure of Example 11 is repeated, except that a 20% solution of potassium ferrocyanide is substituted for the potassium ferricyanide. A dark blue image on a light blue background is produced.

Twenty volumes of solution 1, one volume of solution 2, and V2 volume of solution 3 are mixed. The resulting solution is flow-coated on polyester glass cloth, dried in a vertical position, and exposed to sunlight for 10 seeonds under a photographic negative. A deep grey-black image is obtained by development in a developing solution composed of diamino phenol dihydrochlon'de (Amidol), 7 parts; sodium sulfite, 5 8 parts; potassium bromide, 1.5 parts; water, 950 parts.

Example 14 One part (by volume) of a 7 /2 aqueous alcohol solution (50/ 50 mixture of ethyl alcohol and water) of ammonium dichromate is added to a solution of the resin of Example 2 in methylethyl ketone (containing a small amount of an alcohol soluble nigrosine dye).- The resulting solution is spray coated on an 8" x 10" polyester glass cloth sheet. The sensitized element is then contact-printed through a negative using a carbon arc lamp and an exposure of three minutes. The unexposed.

area is easily removed by immersion in a 1:1 acetone:

water solution, leaving a relief image in the exposed areas of excellent definition and high. durability.

Example 15 Substituting an equivalent amount of each of the resinsof Example '6-for the resin of Example 2, the preceding experiment is repeated. The resulting relief im-. age in each case is an excellent reproduction of thenegative image which can be used in the same'm-anner as bichromate-gelatin sensitized plates in photographic/reproduction processes. i

Example 16 An 8" x 10" sheet of Mylar, coated with the photosensitive composition of Example 2, is exposed, in contact with a positive transparent test sheet, with a shield to give 2, 4, 6, 8, and IOminute areas of exposure to a carbon arc lamp (30 inches from the film). The film is then exposed to a chromalox infrared heater (distance =8-10 inches) for a period of 10 minutes. When the is immersed in a 0.5% caustic developing bath,

marked differential solubility is experienced, in that the" image area Washes out, while the non-image area remains intact.

p-Diethylaminobenzene diazoniumfluoborate 1 The solution is flow-coated on polyester glass cloth, drained, and dried in a vertical position, exposed under a positive obtained by inking designs on a sheet of polyester glass cloth with India ink, to sunlight for one minute, then under a heat lamp for two minutes at a distance of 9 inches. The film is then developed in the developing solution of Example 1 and dipped for 10 seconds in an ammonia solution containing one volume of concentrated (28%) aqueous ammonium hydroxide and 10 volumes of distilled water. The film is then rinsed in water. The image (colored) areas of theprint swell more strongly than the non-image areas and can be rubbed or washed away. The dried print presents an intaglio reproduction of the positive.

' Example 18 The procedure of Example 17 is repeated, except that exposure to the heat lamp is omitted. The non-image areas swell and an intaglio image is obtained.

Example 19 A solution is prepared as follows:

a Parts Methylethyl ketone '180 The resinous copolymer of Example 8 20 the cut-out suffer little or no swelling and preserve the image of the cut-out as relief area of insoluble coating.

After developing and fixing the coatings of photosensi tive compositions of this invention, these coatings are characterized by insolubility in neutral or acidic aqueous solution, i.e., pH of 7 or less, however these coatings become progressively more soluble in aqueous alkaline solutions with increasing pH above 7. Generally, this solubility ranges from very slight at a pH slightly above 7 to ready and complete solubility at a pH of about 13. This solubility-mi aqueous: alkaline solutions can be T reduced in a number fways such as by'addingsignificant amounts of a compatible hydrophobic resin or by postheating (as by exposureto radiant heat) the developed and fiXedcoating; The addition of cross-linking agents, as previous ly described, increases even" more the alkaliresistance of the coating and fixed coating. V V What is claimedi's: 7 u p p -1. A1photographic composition consisting'essentially of a photosensitive material incorporated in a carrier which contains as its sole polymer component a waterinsoluble resinous copolymer; said photosensitive material beingi selected from -the group consisting of light sensitive diazo v,corripounds, dichromates, ironsystems, ironsilver systems, silver salts and mixtures thereof; said resinous-copolymer containing in its formula both (a) polymerized monomers selected from the group consisting of vinyl esters, vi nyl 1 others, acrylonitrile, 1 methacrye loiiitiilqiethacrylonitrileand vinylidene halides, and (b) at leastone polymerized monomer group having a formu- 1a of the group consisting of:

by R and R collectively with the further pro vision at 5:90% ofthe'R and R groups are ester groups of the formula: v

,2; A photographic. composition consisting essentially offa photosensitive material. incorporated in a carrier which contains as its sole polymer component a waterinsoluble resinous copolymer; said photosensitive material beingjselected'ffrom. the group consisting of lightsensitive diazo compounds, Wdichromates, -iron systems, iron- 'sil'ver systems, silver salts and mixtures thereof; said resinous copolymer being a copolymer of (a) a .vinyli-' dene compound selected from the group consisting of vinyl esters, ,vinyl ethers, acrylonitrile, methacrylonitrile; ethacrylonitrile. and vinylidene halides, and (b') --ma1eic anhydride; said copolymer being esterified-with O;1 0'.6 molarrproportion, per molar'proportion-of maleic anhydride; -of;analcohol selected from the group consisting of,-al iphatic alcohols; aromatic, alcohols; and'icyclo aliphaiic QOholsE and. aryl groups, a and ananhydride upon post heatin'g the developed a molar proportion, per molar proportion of maleic dride, ofan alcohol selected from the group consisting of aliphatic alcohols, aromatic alcohols, and cycloaliphatic alcohols.

4. A photographic composition consisting essentially of a light sensitive'diaz-o compound incorporated in a carrier which contains as its sole polymer componental water-insoluble resinous copolymer; said resinous copoly mer being a copolymer of (a) vinyl acetate, and (b) maleic anhydride; said copolymer being esterified with 0.1-0.6 molar proportion, per molar proportion of maleic anhydride, of an alkanol containing 1-8 carbon atoms in its structure. 7

p5. A photographic composition consisting essentially of a light sensitive dichromate compound incorporated in a carrier which contains as its sole polymer component a water-insoluble resinous copolymer; said resinous co-p polymer being a copolymer of (a) vinyl acetate, and (b) maleic anhydride; said copolymer being esterified with 0.1=0.6 molar proportion, per molar proportioii'of maleic anhydride, of an alkanol containing 1-8 carbon atoms in its structure.

6. Themethod of forming a relief image which coinprises; (l) preparing a coated surface by coating a surface with a photographic composition consisting essen: tially of a photosensitive material incorporated in a carrier which contains as its sole polymer component a Water-insoluble resinous copolymer, (2) exposing the coated surface to light with a replica of the relief image interposed between the light source and the coated sur face, and (3) treating the coated surface with a solution to remove the coating composition from the unexposed area; said photosensitive material being selected from the group consisting of light sensitive dichromate compounds and light sensitive'diazo compounds; said resinous vcopolymer containing in formula both (a) polymerized monomers selected from the group consisting of vinyl esters, vinyl ethers, acrylonitrile, methacrylonitrile,.ethacrylonitrile and vinylidene halides,';and (b) at least one polymerized monomer group having a forwhere I is" selected front the groupv consisting of allay] group's; alkoxyalkyl groups, alken'yl' groups, alkinyl 17 groups, cycloalkyl groups and aryl groups, and an anhydride group of the formula:

O=(IJ\ 1:0

formed by R and R collectively with the further provision that 590% of the R and R groups are ester groups of the formula:

(HJOR4 7. A photographic element comprising a surface bearing at least one layer of the photosensitive composition of claim 1.

8. A photographic element comprising a glass fiber reinforced polyester laminate bearing at least one outer lamina of the photosensitive composition of claim 1.

18 9. A photographic element comprising a metal surface bearing at least one layer of the photosensitive composition of claim 1.

10. A photographic element comprising a polyethylene terephthalate surface bearing at least one layer of the composition of claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 1,981,102 Hagedorn et al Nov. 20, 1934 2,616,851 Giammaria Nov. 4, 1952 2,687,958 Neugebauer Aug. 31, 1954 2,719,141 Smith Sept. 27, 1955 2,835,656 Unruh et al May 20, 1958 FOREIGN PATENTS 632,174 Great Britain Nov. 17, 1949 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2390,281 June 27",- 1961 John O. Printy et alq It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patentv should read as corrected below.

Column 2 line 43 for "esters read ester column 9 lines 62 and 74 for "Ben Day'fi each occurrence read. benday column 13 line 9,, for "fluoroborate" read fluohorate line 26 for "Ac tone" read Acetone column l6 lines 56 to 61 the second formula should appear as shown below instead of as in the patent:

$2 -CH :-(f CH 2 3 column 18 under the heading "FOREIGN PATENTS" add the following Q 585 760 Great Britain-Feb 24 1947 Signed and sealed this 12th day of December 1961n (SEAL) Attest: v

ERNEST W. SWIDER DAVID L. LADD Attest ir ig Officer 7 Commissioner of Patents 

1. A PHOTOGRAPHIC COMPOSITION CONSISTING ESSENTIALLY OF A PHOTOSENSITIVE MATERIAL INCORPORATED IN A CARRIER WHICH CONTAINS AS ITS SOLE POLYMER COMPONENT A WATERINSOLUBLE RESINOUS COPOLYMER, SAID PHOTOSENSITIVE MATERIAL BEING SELECTED FROM THE GROUP CONSISTING OF LIGHT SENSITIVE DIAZO COMPOUNDS, DICHROMATES, IRON SYSTEMS, IRONSILVER SYSTEMS, SILVER SALTS AND MIXTURES THEREOF, SAID RESINOUS COPOLYMER CONTAINING IN ITS FORMULA BOTH (A) POLYMERIZED MONOMERS SELECTED FROM THE GROUP CONSISTING OF VINYL ESTERS, VINYL ETHERS, ACRYLONITRILE, METHACRYLONITRILE, ETHACRYLONITRILE AND VINYLIDENE HALIDES, AND (B) AT LEAST ONE POLYMERIZED MONOMER GROUP HAVING A FORMULA OF THE GROUP CONSISTING OF: 